Search NASA⌕ Search

SEARCH · Search NASA

Results for “Absorption”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,207 records · Page 67

High-throughput computational X-ray absorption spectroscopy

X-ray absorption spectroscopy (XAS) is a widely-used materials characterization technique. In this work we present a database of computed XAS spectra, using the Green's formulation of the multiple scattering theory implemented in the FEFF code. With more than 500,000 K-edge X-ray absorption near edge (XANES) spectra for more than 40,000 unique materials, this database constitutes the largest existing collection of computed XAS spectra to date. The data is openly distributed via the Materials Project, enabling researchers across the world to access it for free and use it for comparisons with experiments and further analysis.

36 MATERIALS SCIENCE↗

Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection–absorption spectroscopy

Here we review the recent development of extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy. This method combines the benefits of X-ray absorption spectroscopy, such as element, oxidation, and spin state specificity, with surface sensitivity and ultrafast time resolution, having a probe depth of only a few nm and an instrument response less than 100 fs. Using this technique we investigated the ultrafast electron dynamics at a hematite (α-Fe 2 O 3 ) surface. Surface electron trapping and small polaron formation both occur in 660 fs following photoexcitation. These kinetics are independent of surface morphology indicating that electron trapping is not mediated by defects. Instead, small polaron formation is proposed as the likely driving force for surface electron trapping. We also show that in Fe 2 O 3 , Co 3 O 4 , and NiO, band gap excitation promotes electron transfer from O 2p valence band states to metal 3d conduction band states. In addition to detecting the photoexcited electron at the metal M 2,3 -edge, the valence band hole is directly observed as transient signal at the O L 1 -edge. The size of the resulting charge transfer exciton is on the order of a single metal–oxygen bond length. Spectral shifts at the O L 1 -edge correlate with metal–oxygen bond covalency, confirming the relationship between valence band hybridization and the overpotential for water oxidation. Furthermore, these examples demonstrate the unique ability to measure ultrafast electron dynamics with element and chemical state resolution using XUV-RA spectroscopy. Accordingly, this method is poised to play an important role to reveal chemical details of previously unseen surface electron dynamics.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The stability, electronic structure, and optical absorption of boron-nitride diamondoids predicted with first-principles calculations

Although diamondoids are broadly studied for their fundamental properties and applications, boron-nitride-based diamondoids are scarcely explored.In this report we predict the stability, electronic structure, and optical absorption spectra of six boron-nitride (BN) diamondoids with first-principles methods based on pseudopotential density functional theory and many-body perturbation methods implemented with a real-space formalism. We find that four of them are thermodynamically stable at room temperature, while B10N8H24 and B6N4H16 show thermodynamic instability in molecular dynamics simulations. With the GW approximation, we predicted the ionization energies and electron affinities of BN-diamondoids and find that the evolution of the electronic structure with size does not follow the same trend as diamondoids, owing to the unbalanced numbers of boron and nitrogen atoms. We show strong photoabsorption of BN-triamantane and BN-adamantane in the infrared and visible ranges and analyze the features of low-energy absorption by examining the characteristics of related orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hot Electron-driven Photocatalysis and Transient Absorption Spectroscopy in Plasmon Resonant Grating Structures

Plasmon resonant grating structures provide an effective platform for distinguishing between the effects of plasmon resonant excitation and bulk metal absorption via interband transitions. By simply rotating the polarization of the incident light, we can switch between resonant excitation and non-resonant excitation, while keeping all other parameters of the measurement constant. With light polarized perpendicular to the lines in the grating (i.e., TE-polarization), the photocatalytic reaction rate (i.e., photocurrent) is measured as the angle of the incident laser light is tuned through the resonance with the grating. Here, hot holes photoexcited in the metal are used to drive the oxygen evolution reaction (OER), producing a measurable photocurrent. Using TE-polarized light, we observe sharp peaks in the photocurrent and sharp dips in the photoreflectance at approximately 9° from normal incidence, which corresponds to the conditions under which there is good wavevector matching between the incident light and the lines in the grating. With light polarized parallel to the grating (i.e., TM), we excite the grating structure non-resonantly and there is no angular dependence in the photocurrent or photoreflectance. In order to quantify the lifetime of these hot carriers, we performed transient absorption spectroscopy of these plasmon resonant grating structures. Here, we observe one feature in the spectra corresponding to interband transitions and another feature associated with the plasmon resonant mode in the grating. Both features decay over a time scale of 1–2 ps. Finally, the spectral responses of grating structures fabricated with Ag, Al, and Cu are also presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A neural network-based approach to predicting absorption in nanostructured, disordered photoelectrodes

Disordered nanostructures in photoelectrodes can increase light absorption in photoelectrochemical system designs. Predicting their optical properties is an elusive task due to the immensity of unique configurations and the intrinsic variance of each. A neural network trained from a small subset of simulations can emulate the complex absorption properties of the entire configuration space for a model disordered system with quantifiable accuracy and computational efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excited-state structural dynamics of nickel complexes probed by optical and X-ray transient absorption spectroscopies: insights and implications

Excited states of nickel complexes undergo a variety of photochemical processes, such as charge transfer, ligation/deligation, and redox reactions, relevant to solar energy conversion and photocatalysis. The efficiencies of the aforementioned processes are closely coupled to the molecular structures in the ground and excited states. The conventional optical transient absorption spectroscopy has revealed important excited-state pathways and kinetics, but information regarding the metal center, in particular transient structural and electronic properties, remains limited. These deficiencies are addressed by X-ray transient absorption (XTA) spectroscopy, a detailed probe of 3d orbital occupancy, oxidation state and coordination geometry. The examples of excited-state structural dynamics of nickel porphyrin and nickel phthalocyanine have been described from our previous studies with highlights on the unique structural information obtained by XTA spectroscopy. Furthermore, we close by surveying prospective applications of XTA spectroscopy to active areas of Ni-based photocatalysis based on the knowledge gained from our previous studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application of saturation absorption spectroscopy to study the hyperfine structure of 235U and accurate 235U/238U isotope ratio determinations at 861.031 nm

The uranium transition 5f 3 6d7s 2 ( 5 L 6 ) → 5f 3 7s 2 7p ( 5 K 5 ) at 861.031 nm was studied using saturation absorption spectroscopy. The hyperfine structure of the 235 U isotope was determined by measuring the Doppler-suppressed absorption spectrum, and the hyperfine structure constants were obtained by employing transition-specific line strength theory and spectral fitting. The magnetic-dipole and electric-quadrupole constants were determined to be A = -3.2887 ± 0.1957 mK and B = 31.8712 ± 8.0789 mK for the upper state 5f 3 7s 2 7p ( 5 K 5 ). A theoretical calculation for the hyperfine structure constants of the 235 U isotope was also carried out by the relativistic configuration-interaction (RCI) method, and the obtained values were found to be in agreement with the measured values. In addition, the line profile of 238 U was experimentally investigated for different excitation intensities and modeled using the RCI method for estimating the transition probability and oscillator strength, with various residual broadening mechanisms considered beyond the radiative decay. Finally, we show that these results allow us to make improvements on the precision of spectral measurements using our previously developed technique for isotope ratio determinations in atomic beams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revisiting the K-edge X-ray absorption fine structure of Si, Ge–Si alloys, and the isoelectronic series: CuBr, ZnSe, GaAs, and Ge

Extended X-ray absorption fine structure (EXAFS) has evolved into an unprecedented local-structure technique that is routinely used to study materials’ problems in the biological, chemical, and physical sciences. Like many other experimental techniques, EXAFS also requires that several key atomic parameters must be known a priori before structural information can be quantitatively determined. Utilizing current analytical methods, we revisit the isoelectronic series CuBr, ZnSe, GaAs, and Ge originally studied by Stern et al. during the early development of EXAFS. We demonstrate that the ab initio EXAFS code FEFF accurately predicts the atomic phase shifts and backscattering amplitudes that are primarily functions of the sum of atomic numbers Z along an EXAFS scattering path. We also investigate quantitative fitting and first- and second-shell phase transferability together with problems that arise if a backscattering atom is identified incorrectly in an EXAFS fitting model. Features in the near-edge region, on the other hand, are shown to require a comprehensive treatment of the band structure and density-of-states, including effects of the screened Coulomb interaction between the photoelectron and core hole. Here, we demonstrate that the Bethe–Salpeter equation (BSE) accurately captures the NEXAFS (or XANES) portion of the spectrum for the isoelectronic series in addition to Si and Ge–Si alloys, including within a few eV of the absorption edge, where band structure and excitonic effects are most important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Towards a theoretical understanding of excitonic properties of phthalocyanine thin films. I. Low-temperature exciton absorption spectra

Phthalocyanine (Pc)-based molecular thin films have emerged in recent years as a promising class of organic semiconductor materials for optoelectronic applications owing to their long exciton coherence length and fast exciton diffusion. However, the dependence of their exciton properties on the dimensionality and thermodynamic conditions, presence of metal ions, and effects of chemical modifications to the PC systems is not yet fully understood. As a first step towards a more comprehensive theoretical understanding of the excitonic properties of Pc thin films, we model their low-temperature exciton absorption spectra by employing the Frenkel Hamiltonian. The latter is derived from quantum-chemical estimates of site energies and exciton–exciton couplings. The predicted exciton absorption spectra of octabutoxy phthalocyanine (H 2 OBPc) is found to be strongly dependent on the dimensionality of the model as well as the distance cutoff for including the monomer–monomer exciton coupling. We also caution that the widely used dipole–dipole approximation could substantially overestimate the excitonic coupling between different monomers compared to a more accurate evaluation using the respective transition densities.

36 MATERIALS SCIENCE↗

The electrode–electrolyte interface of Cu via modulation excitation X-ray absorption spectroscopy

The development and application of modulation excitation X-ray absorption spectroscopy with sub-second resolution and better than 0.02% detection sensitivity unveils the kinetics of the anodic oxidation of Cu in bicarbonate electrolytes. Accessing the electrode–electrolyte interface under operating conditions and capturing time-resolved kinetics remain challenging in electrochemical studies. Copper's interfacial oxidation dynamics remain unclear despite extensive research. Modulation excitation X-ray absorption spectroscopy (ME-XAS) was used to probe Cu in 100 mM KHCO 3 with sub-second sensitivity, revealing that hydroxide forms 30 ± 10 ms before the appearance of Cu 2 O at positive potentials (0 to 0.5 V vs. RHE) near open-circuit conditions. From −0.4 to 0.8 V vs. RHE, hydroxide coverage reaches 49%, accompanied by a balanced presence of Cu( i ) and Cu( ii ) oxides. These insights into Cu interfacial redox behavior under intermittent renewable energy operation—relevant to CO 2 electrolyzer durability—enhance our fundamental understanding of electrochemical interfaces.

Garcia-Esparza, Angel T↗

Baryon acoustic oscillations from the cross-correlation of Ly α absorption and quasars in eBOSS DR14

We present a measurement of the baryon acoustic oscillation (BAO) scale at redshift z =2.35 from the three-dimensional correlation of Lyman- α (Ly α ) forest absorption and quasars. The study uses 266 590 quasars in the redshift range 1.77< z < 3.5 from the Sloan Digital Sky Survey (SDSS) Data Release 14 (DR14). The sample includes the first two years of observations by the SDSS-IV extended Baryon Oscillation Spectroscopic Survey (eBOSS), providing new quasars and re-observations of BOSS quasars for improved statistical precision. Statistics are further improved by including Ly α absorption occurring in the Ly β wavelength band of the spectra. From the measured BAO peak position along and across the line of sight, we determined the Hubble distance D H and the comoving angular diameter distance D M relative to the sound horizon at the drag epoch r d : D H ( z =2.35)/ r d =9.20 ± 0.36 and D M ( z =2.35)/ r d =36.3±1.8. These results are consistent at 1.5 σ with the prediction of the best-fit spatially-flat cosmological model with the cosmological constant reported for the Planck (2016) analysis of cosmic microwave background anisotropies. Combined with the Ly α auto-correlation measurement presented in a companion paper, the BAO measurements at z =2.34 are within 1.7 σ of the predictions of this model.

79 ASTRONOMY AND ASTROPHYSICS↗

Attosecond transient absorption instrumentation for thin film materials: Phase transitions, heat dissipation, signal stabilization, timing correction, and rapid sample rotation

We present an extreme ultraviolet (XUV) transient absorption apparatus tailored to attosecond and femtosecond measurements on bulk solid-state thin-film samples, specifically when the sample dynamics are sensitive to heating effects. The setup combines methodology for stabilizing sub-femtosecond time-resolution measurements over 48 h and techniques for mitigating heat buildup in temperature-dependent samples. Single-point beam stabilization in pump and probe arms and periodic time-zero reference measurements are described for accurate timing and stabilization. A hollow-shaft motor configuration for rapid sample rotation, raster scanning capability, and additional diagnostics are described for heat mitigation. Heat transfer simulations performed using a finite element analysis allow comparison of sample rotation and traditional raster scanning techniques for 100 Hz pulsed laser measurements on vanadium dioxide, a material that undergoes an insulator-to-metal transition at a modest temperature of 340 K. Experimental results are presented confirming that the vanadium dioxide (VO 2 ) sample cannot cool below its phase transition temperature between laser pulses without rapid rotation, in agreement with the simulations. The findings indicate the stringent conditions required to perform rigorous broadband XUV time-resolved absorption measurements on bulk solid-state samples, particularly those with temperature sensitivity, and elucidate a clear methodology to perform them.

47 OTHER INSTRUMENTATION↗

Soft x-ray optical constants of sputtered chromium thin films with improved accuracy in the L and M absorption edge regions

In this paper, we determine with improved accuracy the complex index of refraction n = 1 - δ + iβ of sputtered chromium thin films for photon energies ranging from 25 eV to 813 eV. These data include the first absolute measurements of the absorption fine structure near the Cr-L edge. First, we verified by combining Rutherford Backscattering Spectrometry and grazing-incidence x-ray reflectometry that the sputtered thin films were pure Cr with a density consistent with tabulated values. Then, we demonstrated that the Cr surface oxide layer remains stable when the samples are exposed to air for up to 4 years. The Cr absorption coefficient β was determined from the transmittance of freestanding Cr thin films with various thicknesses, measured at the ALS synchrotron radiation source. A model is proposed to correct the transmittance data from the spectral contamination of the source. Finally, we used the new β values, combined with theoretical and tabulated data from the literature, in order to calculate the δ values by the Kramers-Kronig relation. The improvement in the accuracy of β values is demonstrated by the f-sum rule. Finally, an additional validation of the new Cr optical constants (δ, β) is performed by comparing the simulated and experimental reflectance of a Cr/B 4 C multilayer mirror near the Cr-L 2,3 edge.

36 MATERIALS SCIENCE↗

Multiple striated heat fluxes patterns on the EAST first wall generated by lower hybrid wave absorption in the scrape-off layer

Multiple striated heat fluxes on the EAST first wall are observed with lower hybrid wave (LHW) heating on the EAST device. Our analysis indicates that the heat source for the striated heat flux is from LHW absorption in the scrape-off layer (SOL). Magnetic field line tracing from the front of the LHW antenna grills is in good agreement with the striated heat flux profile. In addition the relative intensity of the LHW absorption in the SOL is consistent with the measured striated heat flux. However, the heat flux at inner strike points and outer strike points significantly decreased when the ion cyclotron resonance frequency (ICRF) wave was switched off, while there was no change for the striated heat flux, suggests that the striated heat flux is independent on the injected power to the core plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Modeling L 2,3 -edge X-ray absorption spectroscopy with linear response exact two-component relativistic time-dependent density functional theory

X-ray absorption spectroscopy (XAS) is a powerful tool that can provide physical insights into element-specific chemical processes and reactivities. Although relativistic time-dependent density functional theory (TDDFT) has been previously applied to model the L-edge region in XAS, there has not been a more comprehensive study of the choices of basis sets and density functional kernels available for variational relativistic excited state methods. In this work, we introduce the implementation of the generalized preconditioned locally harmonic residual algorithm to solve the complex-valued relativistic TDDFT for modeling the L-edge X-ray absorption spectra. Further, we investigate the L 2,3 -edge spectra of a series of molecular complexes using relativistic linear response TDDFT with a hybrid iterative diagonalization algorithm. A systematic error analysis was carried out with a focus on the energetics, intensities, and magnitude of L 2 –L 3 splitting compared to experiments. Additionally, the results from relativistic TDDFT calculations are compared to those computed using other theoretical methods, and the multideterminantal effects on the L-edge XAS were investigated.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Intrinsic shape of free carrier absorption spectra in 4H-SiC

Free carrier absorption spectra are measured along the different polarization directions with respect to the c-axis of 4H-SiC using ultrafast differential transmission spectroscopy. Probing of excited carrier spectra in an undoped material reveals intrinsic resonances within the conduction band. Widths of the detected resonance peaks are shown to be wider than their theoretical estimates and more comparable to the ones observed in a low doped material. Relative strength of the peaks, on the other hand, is shown to be nearly excitation independent in contrast to the doping induced absorption weakening for the same transitions in n-type samples. Finally, free carrier cross sections are extracted from the excitation dependency of the detected spectra and linked to the individual electron and hole contributions in the near infrared range.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electrical tuning of a terahertz quantum cascade laser based on detuned intersubband absorption

A mechanism to electrically tune the frequency of terahertz quantum cascade lasers (QCLs) is developed that allows for tuning, while the QCL is operated close to its peak bias and temperature. Two optically coupled but electrically isolated cavities are used in which the bias of a control cavity tunes the resonant-mode of the coupled QCL cavity independent of the QCL's operating bias. Approximately 4 GHz electrical tuning is realized for a 3.6 THz distributed-feedback QCL operating in pulsed mode at 58 K in a Stirling cooler. The single-mode QCL emits near-constant peak-power in the range of 5$-$5.3 mW through the tuning range and radiates in a narrow single-lobed beam with a far-field divergence of ~4°×11°. The superlattice structure of the QCL is designed to implement a low-voltage intersubband absorption transition that is detuned from that of its gain transition, the strength of which could be controlled sensitively with applied voltage utilizing resonant-tunneling injection of electrons in the absorption subband. Finally, the tuning is realized by the application of small bias voltages (~6$-$7 V) and requires a narrow bias range (~1 V, ~40 A/cm 2 ) to traverse across the entire tuning range, and the method should be generally applicable to all intersubband lasers including mid-infrared QCLs.

42 ENGINEERING↗

Time-resolved x-ray absorption spectroscopy probe in ultrafast surface chemistry

To celebrate the scientific achievement of Jo Stöhr, I present here a personal account of the use of x-ray absorption spectroscopy to probe dynamics on surfaces using x-ray lasers. In particular, I will review the investigation of ultrafast processes in adsorbates on surfaces using an optical pump and an x-ray absorption spectroscopy probe. Here, it is shown that it is possible to gain insight into the effects of electronic excitations in metals on adsorbates as well as laser-induced vibrational motions. Furthermore, the ultrafast optical pump allows the detection of the CO precursor state in the desorption channel, species close to the transition state in CO oxidation, and the transient HCO intermediate during CO hydrogenation on Ru(0001).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗